Aggregation‐induced improvement of catalytic activity by inner‐aggregate electronic communication of metal‐fullerene‐based surfactants

verfasst von

Marius Kunkel, Stefan Bitter, Frank Sailer, Rainer F. Winter, Sebastian Polarz

Abstract

A paradigm for active constituents in (homogeneous) catalysis is that optimum performance requires maximum dispersion. Generally, aggregation results in a decline. This is a different case in supramolecular catalysis. A new concept based on surfactants equipped with functional heads is presented, which becomes a more active catalyst itself upon aggregation. The head group of the surfactants is composed of a diethylenetriamine-functionalized fullerene capable of coordinating to catalytically active metals like Co

^II. The improvement of catalytic properties upon aggregation is demonstrated via electrocatalytic water-splitting reaction as a model system. Detailed electrochemistry studies were performed at concentrations below and above the critical aggregation concentration (cac). While isolated surfactant molecules represent only moderately active catalysts, drastic improvement of efficiency in the hydrogen evolution (HER) as well as in the oxygen evolution reactions (OER) were detected, once vesicular structures have formed. Self-organization of the surfactants leads to an increase in turnover frequencies of up to 1300 % (HER). The strongly beneficial effect of aggregation arises from the favorable alignment of individual molecules, thus, facilitating intermolecular charge transfer processes in the vesicles.

Organisationseinheit(en)

Institut für Anorganische Chemie

Externe Organisation(en)

Universität Konstanz

Typ

Artikel

Journal

CHEMCATCHEM

Band

Seiten

2726-2731

Anzahl der Seiten

ISSN

1867-3880

Publikationsdatum

20.05.2020

Publikationsstatus

Veröffentlicht

Peer-reviewed

ASJC Scopus Sachgebiete

Katalyse, Anorganische Chemie, Physikalische und Theoretische Chemie, Organische Chemie

Ziele für nachhaltige Entwicklung

SDG 7 – Erschwingliche und saubere Energie

Elektronische Version(en)

https://doi.org/10.1002/cctc.202000412 (Zugang: Offen)